|Publication number||US5349188 A|
|Application number||US 07/506,391|
|Publication date||Sep 20, 1994|
|Filing date||Apr 9, 1990|
|Priority date||Apr 9, 1990|
|Also published as||CA2069392A1, CA2069392C, DE69107467D1, DE69107467T2, DE69107467T3, EP0555216A1, EP0555216B1, EP0555216B2, US5349189, WO1991015762A1|
|Publication number||07506391, 506391, US 5349188 A, US 5349188A, US-A-5349188, US5349188 A, US5349188A|
|Inventors||Steven M. Maggard|
|Original Assignee||Ashland Oil, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (12), Non-Patent Citations (12), Referenced by (56), Classifications (12), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Cross references to related application: U.S. patent application 402,959, filed Sep. 1, 1989 now U.S. Pat. No. 4,963,745, issued Oct. 16, 1990 relates to the general field of the present invention.
I. Field of the Invention
The present invention relates to techniques of analysis, particularly of hydrocarbon and substituted hydrocarbon mixtures, generally classified in U.S. Class 250.
II. Description of the Prior Art
Many prior teachings of the determination of the individual components of paraffins, isoparaffins, aromatics, napthenes, and olefins (PIANO) have been taught in prior literature and patents. A preferred prior technique is gas chromatography, wherein a sample is injected into an absorbant column swept by an elutriating inert gas, e.g. helium, and the elapsed time for arrival at the end of the column is measured for each of the components, e.g. by a flame ionization detector, thermal conductivity detector, or other detector.
Conventionally, the percents of each of the individual compounds detected by gas chromatography are grouped under their respective generic classifications in the PIANO classification system, and the relative percentage of each of the components paraffins through olefins is determined in weight percent, volume percent, or mole percent as required. An example of this procedure is that taught by Analytical Automation Specialists, Inc., "The Detailed Analysis of Petroleum Naphthas, Reformates, Gasoline and Condensates by High-Resolution Gas Chromatography", Operators Manual, P.O. Box 80653, Baton Rouge, La. 70898. Also available in AAS (Analytical Automated Systems) PIANO Software Package, Sievers Research PIANO Software Package.
Recently, near-infrared (NIR) spectrophotometric analysis has been used to determine baking quality of flour, digestibility of forages, and other physical properties of samples, e.g. in U.S. Pat. No. 4,800,279 to Hieftje, Honigs, and Hirschfeld, and a number of the references cited therein.
Other NIR analysis techniques are taught in J. Prakt. Chem., 317(1), 1-16 by Bernhard and Berthold, who perform structural group analysis of mixtures of saturated and aromatic hydrocarbons, and in the quantitative analysis of benzene-toluene-paraffin mixtures in the near-infrared by Leimer and Schmidt in Chem. Tech. (Leipzig), 25(2), 99-100.
Near-infrared spectroscopy of hydrocarbon functional groups was performed by Tosi and Pinto, Spectrochim ACTA, Part A, 28(3), 585-97, who examined 50 linear and branched paraffins and related the absorbtivities to the concentration of the groups such as CH3 and CH2.
Ultraviolet and Near-infrared analysis of mixtures of aromatics is taught by Schmidt in Erdoelkohle, Erdgas, Petrochem., 21(6), 334-40, who sought to determine concentration of specific compounds, not the groups (aromatic, etc.) measured by this invention, and used different wavelengths.
Kelly, Barlow, Jinguji and Callis of the University of Washington, Seattle, (Analytical Chem. 61, 313-320,) found gasoline octane numbers could be predicted from near infrared absorbance in the range 660-1215 nanometers (nm). They found best correlation between absorbance and octane number to occur at 896, 932 and 1164 nm for research octane number, 930, 940 and 1012 nm for motor octane number, and 896, 932 and 1032 nm for pump octane number. Kelly does not teach PIANO analysis, and only uses the short wavelength near-infrared, 660-1220 run, but did determine the aromatic, olefin, and saturate (paraffins plus isoparaffin) content of gasolines. However, Kelly used a very limited number of samples (nine) and restricted their measurements to the short wavelength near infrared (660-1220 nm), unlike the present invention. Furthermore, they did not disclose which wavelengths correlated with aromatic, olefin, or saturate concentrations. Example 6 compares this Kelly work. Thus Kelly does not enable one skilled in the art to practice the present invention nor to attain its advantages.
None of above teach PIANO analysis of the more complex mixtures routinely encountered in petroleum refineries. Such mixtures almost always contain both aromatics and olefins which are generally thought to have overlapping absorbance wavelengths in the mid-infrared region, suggesting that their overtones and combination bands in the near-infrared region would also overlap, and preclude determination of their individual concentrations in the mixtures.
Such mixtures are often very complex; gasoline mixtures frequently contain over 300 compounds.
Also, individual molecular groups found (e.g. methylene) in napthenes, are also found in paraffins and also in isoparaffins, as well as in substituted aromatic compounds, and also in olefins, further compounding the difficulty of analyzing for concentration of individual PIANO components.
The present invention utilizes a combination of selected NIR wavelengths in which measurements of absorbance are made and combines these with multiple regression analysis and modeling to differentiate the concentration of individual PIANO components.
FIG. 1 is a plot of the second derivative of absorbance versus wavelength for a simulated complex mixture. The simulation is accomplished by super-imposing a plot of alpha-olefins on plots of paraffins, isoparaffins, aromatics and napthenes. As can be seen, olefins have several characteristic wavelength ranges which can be used to determine their concentration. It can be seen from FIG. 1 that the olefins should be distinguishable from the other PIANO components, isoparaffins, paraffins, etc. in the wavelength region of 2050 to 2250 nm.
Complex mixtures, such as gasolines and reformates, have 5 total degrees of freedom for a PIANO analysis by NIR (one for each of the PIANO components). Since the degrees of freedom for a mathematical model must be less than the total number of degrees of freedom, a maximum of four wavelengths can be used in the model. However, it should be noted that some experimenters might wish to use more or less wavelengths. Each PIANO constituent has its own model in the present invention. In the case of paraffins and isoparaffins, no characterizing wavelength has been found in the near infrared region because of overlapping absorbances of the other PIANO constituents, and therefore their concentrations must be solved for using the four degrees of freedom and by using four different wavelengths. Experimentally it has been found useful to isolate portions of the near infrared spectra where paraffins and isoparaffins can be distinguished. The following wavelengths are most useful for the determination of paraffin and isoparaffin concentrations: 880-974, 1152-1230, 1320-1380, 1470-1578, 1614-1644, 1746-1810, 1940-2000, and 2058-2130 run. For the case of aromatics, napthenes, and olefins, however, it is possible to identify characteristic portions of the spectra where these constituents can be identified as shown in FIGS. 1-5. As a result of this, only three degrees of freedom are needed to determine the concentration of each of these constituents, and hence only three wavelengths are needed. Because it is possible to isolate characteristic wavelengths for these constituents, it ensures that the predicted concentrations are truly related to the PIANO constituent of interest.
This invention will find greatest application in the petroleum refining industry. For example, it can be used to monitor the aromatic content of gasolines, diesel fuel, and jet fuel. Another potential application is to feed the aromatic and olefin concentrations of gasoline or gasoline blending streams into a blending program such as Ashland Petroleum's BOSS (Blend Optimization and Scheduling System), Chevron's GINO (Gasoline In-Line Optimization), Oil Systems, Inc., MGBlend, or other similar blending optimization programs. Other applications of the invention include various catalytic processes such as catalytic reforming where a knowledge of feedstock composition and product composition could be used to determine reactor severity and in the optimization of the unit. PIANO composition of fluid catalytic cracking bottoms is another application. The characteristic PIANO wavelengths can also be used to make predictions of octanes. For example, wavelengths which are indicative of aromatic concentration can also be used to predict the octane of reformates since it is the aromatic content which predominately determines the octane. Similarly alpha-olefin content was found to be highly correlated with the motor octane of Ashland summer blended gasolines.
There are also an enormous number of applications of PIANO analyses outside of the petroleum industry. For example, the monitoring of alpha-olefin concentration during cationic polymerization reactions in the detergent industry. Also the invention could be used to monitor the purity of various streams, the concentration changes which occur during a chemical reaction, and even impurity concentrations of PIANO constituents.
As those skilled in the art will be aware, the absorbance signal from the measurement of the characteristic PIANO bands, used either solely or in conjunction with other bands, will preferably be mathematically processed to provide derived signals which are indicative of the concentrations (or property) being measured. Preferred techniques for mathematical processing are absorbance base-line offset corrected absorbance data; taking the first, second, third, fourth or higher derivative of the absorbance spectrum; the technique of dividing the absorbance at one wavelength by another; spectral subtraction; and various combinations of these mathematical techniques. Also valuable are the well-known curve fitting techniques of Savitsky-Golay and Kubelka-Munk, and N-point smoothing (signal averaging). Other types of statistical data treatment are also possible such as partial least squares (PLS), Gauss-Jordan Row reduction, etc.
By equivalent to weighting constant, we mean to include among other techniques known to the art the wavelength coefficients of partial least squares regression and principal component regression and the constants obtained from the Gauss-Jordan row reduction algorithm. (See Harald Martens and Tormod Naes, Multivariate Calibration, John Wiley & Sons; New York, 1989 [ISBN 471-90979-3], and Honigs, D. E., Heiftje, G. M.; Hirschfeld, T., Applied Spectroscopy, 38(3), 1984, p. 317.) Also any constant obtained from any statistical calibration used to calculate values for unknown samples.
The techniques of the present invention are also highly useful for the objectives of aforementioned copending U.S. Ser. No. 402,959, filed Sep. 1, 1989 relating to the determination of research, motor and pump octane (also including cetane number of diesel fuels). Example 4 shows the invention predicting research octane number of reformate.
Measuring octane number, including any other measure of knock avoidance, of fuels by near infrared range spectroscopy, the present invention takes the octane number by:
(a) measuring at at least one wavelength, the near infrared absorbance in the bands of:
1. for napthenes: 1672-1698 and/or 1700-1726 nanometers (nm);
2. for olefins: 1622-1650 and/or 2064-2234 nm;
3. for aromatics: 1092-1156 and/or 824-884 and/or 1656-1692 nm;
4. for paraffins and isoparaffins: 880-974, 1152-1230, 1320-1380, 1470-1578, 1614-1644, 1746-1810, 1940-2000, and/or 2058-2130 nm.
(b) taking each of the absorbances measured, or a mathematical function thereof,
(c) performing multiple regression analysis partial least squares analysis, or other statistical treatment using the above absorbances or functions as individual independent variables,
(d) assigning and applying weighting constants or their equivalents to said independent variables,
(e) applying the above steps using known compositions to calibrate the instrument and determine said weighting constants or equivalents,
(f) repeating said steps with unknown compositions, applying the weighting constants or equivalents determined during said calibration with known compositions.
The flow may flow substantially intermittently or continuously past the point where the measurements are being made. The mathematical function may be a first, second, or third, etc. derivative of said absorption of said band being measured, the fuel may preferably be a gasoline blending stream, and the octane measured may preferably be research octane, more preferably motor octane, and most preferably pump octane.
As discussed briefly below and in the copending application aforementioned, the signal may control a fuel blending system feeding blending components having different octane numbers into a common zone, whereby a fuel product having a desired octane is produced.
Near Infrared spectrometers, Fourier Transform near infrared spectrometers, and modified IR spectrometers of conventional design may be used with the invention. Preferred modes of operation are transmission, reflectance, and transflectance. Suitable spectrometers are the NIR Systems Model 6500; LT Industries Model 1200; and the Guided Wave Model 300 Series. The spectrometer can be operated in a quality control lab, on a batch basis (receiving signals, e.g. by a sample feeding arrangement), or, more preferably, on a continuous basis in which the fluid to be measured flows through a cell or in which a probe immersed in the flowing fluid transmits optically through a fiber-optic cable to the spectrophometer. The techniques for sampling, measuring, and signal processing can be conventional and are well known to those skilled in the art.
Blending systems for use with the present invention to provide blends having desired PIANO analyses can be of conventional design, usually involving the use of proportioning pumps or automatic control valves which control the addition rate for each of a series of components fed from different tanks or other sources. A computer receiving the output signal from the spectrophotometer can readily process the information to not only provide the target PIANO analysis or octane number in the finished blended hydrocarbon, e.g. gasoline, but also to provide the target blend at minimum cost, given the relative costs and octane or PIANO enhancement values of the components being fed to the blending system.
The present invention permits the determination of PIANO components which have previously been determined only by laboratory analysis or by relatively long gas chromatography techniques. The invention permits this determination of different components to be made simultaneously and nearly continuously, providing on-line (or at-line) analysis without the need to return samples to control labs in refineries.
FIG. 1 is a plot of the second derivative of absorbance versus wavelengths for olefins superimposed on other PIANO constituents from 2050 to 2250 nm.
FIG. 2 is a similar plot from 1550 to 1750 nm. An aromatic band is also present in this Figure.
FIG. 3 is a similar plot showing aromatics superimposed on other PIANO constituents from 800 to 900 nm.
FIG. 4 is a similar plot showing aromatics superimposed on other PIANO constituents from 1050 to 200 nm.
FIG. 5 is a similar plot showing napthenes superimposed on other PIANO constituents from 1650 to 1750 nm.
FIG. 6 shows the volume percent aromatics as measured by gas chromatography (GC-PIANO) versus the volume percent predicted according to the present invention in Example 2.
FIG. 7 is plot of reformate research octane predicted by NIR versus a knock engine from Example 4.
FIG. 8 is a plot of motor octanes predicted by the present invention versus a knock engine from Example 5.
Mixtures containing PIANO components as follows are analyzed according to the techniques of the present invention:
______________________________________paraffin 8.86-32.7 % by volumeisoparaffin 19.1-51.8aromatics 13.0-68.0napthenes 0.509-21.6olefins 0.00-17.7______________________________________
The samples include gasolines, stabilized reformates, unstabilized reformates, naphtha, and catalytically cracked bottoms.
The apparatus is an NIR System Model 6500 Near Infrared Spectrophotometer measuring approximately 200 samples of hydrocarbons each containing PIANO components. The wavelengths used and the range of volume percents are shown in Table 1. Approximately 50 of the samples were separated out as a calibration set, selected so as to represent a increasing concentration of each of the PIANO constituents so that the entire range was covered.
A multiple regression analysis was performed on the second derivative of the absorbances measured at the indicated wavelengths. The regression coefficients are as shown in Table 2, with the multiple coefficients of correlation being as shown in Table 1.
The standard errors of the estimate (calculated by well-known statistical techniques) for this calibration set are shown in Table 1.
The remaining 150 samples are used as a prediction set (for prediction of PIANO in unknown samples). Again, the second derivative of the absorbances are used as the independent variables in a multiple regression analysis using the weighting constants determined from the calibration set and shown in Table 2, using NIR System's computer program (NIR Spectral Analysis Software) for multiple regression analysis supplied with the apparatus, though SAS or other well-known statistical programs could be used instead. These programs multiply the second derivative of each absorbance at each wavelength by its respective weighting constant and sum the products and the regression constant to provide a weighted value which is characteristic of the predicted percent of each respective PIANO component, e.g. the standard error of prediction is shown in the far right column of Table 1.
Comparing the standard error of estimate with the standard error of prediction, it can be seen that the actual standard error of prediction shows excellent correlation between the model and the actual concentrations.
TABLE 1__________________________________________________________________________Results of PIANO Analysis of Stabilized Reformates,Unstabilized Reformates, Gasolines, Reformer Feed(Naphtha), and Catalytically Cracked Bottoms Std Error Std Error Wavelengths, Range of Values Mult. of Est. or Pred.Component nm Vol. % Corr. Vol. % Vol. %__________________________________________________________________________Paraffins 1468,1934,1986 8.86-32.7 0.9837 0.869 0.915 & 2058Isoparaffins 1384,1648,1230 19.1-51.8 0.9903 1.18 1.02 & 1062Aromatics 2062,1148,1908 13.0-68.0 0.9994 0.540 0.593Napthenes 1710,1428,1496 0.509-21.6 0.9839 0.800 0.591Olefins 2114,2148,1638 0-17.7 0.9802 1.04 0.467__________________________________________________________________________
TABLE 2__________________________________________________________________________Multiple Regression Coefficients for Prediction ofPIANO Concentrations and Octanes PIANO Analysis of Reformates, PIANO Analysis of Motor Octane Research Octane Catalytically Cracked Reformates, (Stab. Number of Number of Bottoms, Naphtha, & Gas. and Unstab.) Gasolines Reformates__________________________________________________________________________Regression ConstantParaffins -41.45 -1.422Isoparaffins -4.244 -99.99Aromatics 9.474 91.76 78.28 288.6Napthenes 11.10 9.645Olefins 17.48 -18.82Regression Coefficient(wavelength)Paraffins 721.3 (1468) -3878 (1288)Isoparaffins -180.5 (1384) 1261 (1330)Aromatics 172.3 (2062) -14.56 (1148) 14.96 (1220) 80.10 (1220)Napthenes -20.61 (1710) -207.1 (1420)Olefins -33.42 (2114) -48.51 (1636)Regression Coefficient(wavelength)Paraffins -143.7 (1934) 716.4 (1468)Isoparaffins 24.06 (1648) -4562 (858)Aromatics -67.6 (1148) 161.5 (2060) -8.474 (2092) -185.2 (1130)Napthenes -213.7 (1428) 11.91 (1678)Olefins -29.94 (2148) 1448 (1312) -8.474 (2092)Regression Coefficient(wavelength)Paraffins 192.8 (1986) 716.4 (1468)Isoparaffins -275.8 (1230) 147.1 (1190)Aromatics -95.73 (1908) 83.40 (1196) -- -4493 (1572)Napthenes -337.3 (1496) 500.4 (1538)Olefins -49.41 (1638) -103.9 (1454)Regression Coefficient(wavelength)Paraffins -105.2 (2058) 133.9 (2048)Isoparaffins 4716 (1062) -2478 (1020) -- --__________________________________________________________________________
When the procedure of Example 1 is repeated on just the stabilized and unstabilized reformate samples, a much greater level of accuracy can be achieved. For example, approximately 25 reformate samples were selected to be used in a calibration set. They were chosen on the basis that they uniformly covered the range of PIANO constituent concentrations. Multiple linear regression was performed on the calibration set using the wavelengths shown in Table 3. The regression coefficients and constant are shown in Table 2. FIG. 6 is a plot of the actual volume percent of aromatics (determined by GC-PIANO) versus the value predicted by the present invention for the calibration data. This data was then used to predict the PIANO concentrations of approximately 125 unknowns. Excellent agreement can be seen between the standard errors of the estimate and the standard errors of prediction in Table 3. High correlations are also observed with the exception of the olefins. This is a result of the low range of olefins in the samples in spite of their low errors of prediction.
TABLE 3__________________________________________________________________________Results of PIANO Analysis of Stabilized andUnstabilized Reformates Std Error Std Error Wavelengths, Range of Values Mult. of Est. or Pred.Component nm Vol. % Corr. Vol. % Vol. %__________________________________________________________________________Paraffins 1288,1468,890 8.86-21.5 0.9889 0.465 0.492 & 2048Isoparaffins 1330,858,1190 19.1-40.0 0.9964 0.666 0.774 & 1020Aromatics 1148,2060,1196 35.9-68.0 0.9995 0.342 0.494Napthenes 1420,1678,1538 0.509-8.83 0.9875 0.296 0.359Olefins 1636,1312,1454 0-3.89 0.7803 0.627 0.418__________________________________________________________________________
When the procedure of Example 1 is repeated on the same samples but substituting partial least squares regression analysis for the multiple regression analysis utilized in Example 1, results are obtained which are shown in Table 4.
The predictions are not as accurate as those of Example 1. An entire area of the spectrum is generally used rather than single wavelengths. For example, for aromatics, the wavelength range from 826 to 1152 nm is used using four latent variables. The four latent variables correspond to the four degrees of freedom for the model. The calibration set for this example includes approximately 50 stabilized and unstabilized reformates, naphthas, and catalytically cracked bottoms and gasolines and the results appear in Table 4. The predictions set include approximately 150 samples of similar hydrocarbon mixtures. Four latent variables were used for each model.
Referring to Table 4, excellent agreement between the standard errors of prediction and the estimate can be seen, showing that the wavelength ranges are indeed highly correlated with their respective PIANO group constituents. It should be possible to obtain even better correlations if the wavelength ranges are further optimized by including other portions of the NIR spectrum.
TABLE 4______________________________________Results of PIANO Analysis by Partial LeastSquares Analysis for Stabilized and UnstabilizedReformates, Naphtha, Gasolines Std Error Std Error Wavelength Mult. of Est. or Pred.Component Range, nm Corr. Vol. % Vol. %______________________________________Aromatics 826-1692 .995 1.63 1.16Napthenes 1672-1726 .973 1.03 0.770Olefins 1622-2200 .989 0.771 0.603Paraffins 880-2130 .957 1.39 1.53Isoparaffins 880-2130 .975 1.85 1.18______________________________________
Applying the process of Example 2 to about 150 samples of a reformate produced by a bench scale reformer operating on Arabian light naphthas, the samples are divided into a calibration set of approximately 50 samples and a prediction set of about 100 samples. The calibration set is chosen to cover a range of research octane numbers from 73 to 102. Multiple regression is preformed on the second derivatives of the absorbances at 1220, 1130 and 1572 nanometers, and a multiple correlation of 0.998 is observed. The calibration samples show a standard error of estimate of 0.505 research octane numbers, and the prediction set shows a standard error of prediction of 0.526 research octane units. This compares favorably to ASTM method D2699 for operation of knock engines which shows a standard error of greater than 0.6 research octane numbers (error estimates are not given for below 80 research octane numbers). The results of the analysis are summarized in Table 5.
TABLE 5__________________________________________________________________________Octane Results for Reformates and Gasolines Range of Std Error Std Error ASTM Allow. Type of Values Mult. of Est. of Pred. Error,Substance Octane Octane No. Corr. Vol. % Vol. % Octane No.__________________________________________________________________________Reformate RON 73-102 0.9980 0.505 0.526 >0.6Gasoline MON 80-91 0.9924 0.362 0.412 0.6__________________________________________________________________________
139 gasoline samples each analyzed for motor octane number by ASTM D2700, and with the samples uniformly covering the octane range from 80.0 to 90.5 motor octane numbers. These samples are analyzed by using the "jack-knife" technique of calibration, wherein the odd numbered samples are placed into a calibration set, and the even numbered samples are used as a prediction set. Regression was performed on the second derivative of the absorbances at these wavelengths using 1220 nm and the olefin absorbance at 2092 nm. The standard error of estimate is 0.362 and the standard error of prediction is 0.412, both in motor octane numbers. Again, this shows excellent agreement with the results obtained by the ASTM method which has a standard error of prediction of 0.600. The results of the analysis are summarized in Table 5.
To demonstrate the improvements to be gained from the use of the current invention, a comparison is made between the current invention and values reported by Kelly et. al., in the literature (Analytical Chemistry, 61, p. 313, 1989 [Table VI]). They report results for aromatics, olefins, and saturates (paraffins plus isoparaffins) using short wavelength near infrared and obtain standard errors of calibration of ±0.42, ±0.57, and ±0.73 and multiple correlation coefficients of 0.998, 0.996, and 0.996, for nine gasoline samples using three wavelengths per each PIANO constituent for aromatics, olefins and saturates, respectively.
To compare the current invention to Kelly et. al., nine gasoline samples are selected and analyzed by GC-PIANO and NIR-PIANO. These samples are chosen on the basis of having the greatest range of each PIANO constituent of the gasoline samples. The actual range of constituents values, wavelengths, standard errors of estimate and multiple correlations appear in Table 6. The results in Table 6 show that higher correlations and lower standard errors are seen for the results obtained using the present invention. In fact, for saturates, aromatics, and olefins, the standard errors of the estimate are all decreased by well over 50%.
TABLE 6__________________________________________________________________________PIANO Regression Results Obtained onthe Nine Gasoline Samples Range of Values Wavelengths Std Error Mult. Corr.Constituent Vol. % nm of Est. Coefficient__________________________________________________________________________Paraffins 12.9-22.0 1894,1230,2124 0.0721 0.9998Isoparaffins 33.7-51.6 1220,1289,2400 0.0978 0.9999Aromatics 17.5-39.7 1660,2368,2350 0.137 0.9999Napthenes 1.65-10.1 1684,2314,1228 0.296 0.9973Olefins 0.823-17.7 2092,862,1350 0.101 0.9999Saturates 50.5-66.7 1162,2376,2130 0.319 0.9990__________________________________________________________________________
Specific compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variation on these compositions, methods, or embodiments are readily apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein.
Reference to copending applications made in the specification is intended to result in such applications being expressly incorporated herein by reference including any patents or other literature references cited within such documents.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3505857 *||Feb 20, 1969||Apr 14, 1970||British Petroleum Co||Analysis of gasoline blending components|
|US4277326 *||Nov 19, 1979||Jul 7, 1981||Exxon Research & Engineering Co.||Oxygen alkylation of phenol-containing hydrocarbonaceous streams|
|US4323777 *||May 19, 1980||Apr 6, 1982||Infrared Industries, Inc.||Hydrocarbon gas analyzer|
|US4433239 *||Feb 12, 1981||Feb 21, 1984||Petro-Canada Exploration Inc.||Method and apparatus for on-line monitoring of bitumen content in tar sand|
|US4448530 *||Feb 23, 1981||May 15, 1984||Schmitt Albert||Spectrophotometer|
|US4591718 *||Oct 25, 1983||May 27, 1986||The United States Of America As Represented By The United States Department Of Energy||Photothermal method for in situ microanalysis of the chemical composition of coal samples|
|US4800279 *||Sep 13, 1985||Jan 24, 1989||Indiana University Foundation||Methods and devices for near-infrared evaluation of physical properties of samples|
|US4963745 *||Sep 1, 1989||Oct 16, 1990||Ashland Oil, Inc.||Octane measuring process and device|
|US5131746 *||Jan 22, 1991||Jul 21, 1992||The United States Of America As Represented By The United States Department Of Energy||On-line process control monitoring system|
|EP0285251A1 *||Feb 25, 1988||Oct 5, 1988||Bp Oil International Limited||Method for the direct determination of octane number|
|EP0304232A2 *||Aug 11, 1988||Feb 22, 1989||Bp Oil International Limited||Method for the direct determination of physical properties of hydrocarbon products|
|GB2217838A *||Title not available|
|1||"Advances in Near Infrared Analyzer Technology" Dr. H. Mark & Dr. G. Kemeny, Feb. 1991 Chemical Processing, pp. 54-58.|
|2||"Determination of Carbon-Hydrogen Groups in High Molecular Weight Hydrocarbons", A. Evans & R. R. Hibbard, Analytical Chemistry, vol. 23, No. 11, Nov. 1951, pp. 1604-1610.|
|3||"Nondestructive Analytical Proc. for Simultaneous Estimation of the Major Classes of Hydrocarbon Constituents of Finished Gasolines," Kelly et al., Anal. Chem. 1990, 62, pp. 1444-1451.|
|4||*||Advances in Near Infrared Analyzer Technology Dr. H. Mark & Dr. G. Kemeny, Feb. 1991 Chemical Processing, pp. 54 58.|
|5||*||Determination of Carbon Hydrogen Groups in High Molecular Weight Hydrocarbons , A. Evans & R. R. Hibbard, Analytical Chemistry, vol. 23, No. 11, Nov. 1951, pp. 1604 1610.|
|6||Louw et al., "A Simple Directly Combined Gas Chromatographic Infrared Spectrometric System for Identification of Low, Molecular Weight Hydrocarbons", Applied Spectroscopy, 29 (1), 1975, pp. 15-24.|
|7||*||Louw et al., A Simple Directly Combined Gas Chromatographic Infrared Spectrometric System for Identification of Low, Molecular Weight Hydrocarbons , Applied Spectroscopy, 29 (1), 1975, pp. 15 24.|
|8||LT Appl. Note, Industry: Petroleum, "Determination of Octane Number by NIR," LT Industries, Rockville, Md.; undated.|
|9||*||LT Appl. Note, Industry: Petroleum, Determination of Octane Number by NIR, LT Industries, Rockville, Md.; undated.|
|10||Maris et al, "Nonlinear Multicomponent Analysis by Infrared Spectrophotometry", Anal. Chem., 55 (1983), pp. 1694-1703.|
|11||*||Maris et al, Nonlinear Multicomponent Analysis by Infrared Spectrophotometry , Anal. Chem., 55 (1983), pp. 1694 1703.|
|12||*||Nondestructive Analytical Proc. for Simultaneous Estimation of the Major Classes of Hydrocarbon Constituents of Finished Gasolines, Kelly et al., Anal. Chem. 1990, 62, pp. 1444 1451.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5412581 *||Nov 5, 1992||May 2, 1995||Marathon Oil Company||Method for measuring physical properties of hydrocarbons|
|US5504331 *||Oct 15, 1993||Apr 2, 1996||Atlantic Richfield Company||Spectroscopic analyzer operating method|
|US5596196 *||May 24, 1995||Jan 21, 1997||Ashland Inc.||Oxygenate analysis and control by Raman spectroscopy|
|US5641962 *||Dec 5, 1995||Jun 24, 1997||Exxon Research And Engineering Company||Non linear multivariate infrared analysis method (LAW362)|
|US5684580 *||May 1, 1995||Nov 4, 1997||Ashland Inc.||Hydrocarbon analysis and control by raman spectroscopy|
|US5712481 *||Jul 23, 1996||Jan 27, 1998||Ashland Inc||Process and apparatus for analysis of hydrocarbon species by near infrared spectroscopy|
|US5751415 *||May 13, 1996||May 12, 1998||Process Instruments, Inc.||Raman spectroscopy apparatus and method for continuous chemical analysis of fluid streams|
|US5892228 *||Sep 30, 1996||Apr 6, 1999||Ashland Inc.||Process and apparatus for octane numbers and reid vapor pressure by Raman spectroscopy|
|US5893727 *||Aug 13, 1996||Apr 13, 1999||Trw Inc.||Method for manufacturing a massive parallel interconnection attachment using flexible circuit|
|US5898056 *||Sep 10, 1996||Apr 27, 1999||Solvay (Societe Anonyme)||Process and device for monitoring the quality of latices of halogen-containing vinyl polymers|
|US5942754 *||Nov 27, 1995||Aug 24, 1999||Kyoto Dai Ichi Kagaku Co., Ltd.||Method of and apparatus for determining hydrogen peroxide|
|US5970424 *||Apr 29, 1996||Oct 19, 1999||Kaffka; Karoly||Method and apparatus for qualifying an object|
|US6028667 *||Jan 14, 1999||Feb 22, 2000||Process Instruments, Inc.||Compact and robust spectrograph|
|US6100975 *||Apr 3, 1998||Aug 8, 2000||Process Instruments, Inc.||Raman spectroscopy apparatus and method using external cavity laser for continuous chemical analysis of sample streams|
|US6121628 *||Mar 31, 1999||Sep 19, 2000||Siemens Westinghouse Power Corporation||Method, gas turbine, and combustor apparatus for sensing fuel quality|
|US6140647 *||Dec 19, 1997||Oct 31, 2000||Marathon Ashland Petroleum||Gasoline RFG analysis by a spectrometer|
|US6159255 *||Dec 11, 1998||Dec 12, 2000||Sunoco, Inc. (R&M)||Method for predicting intrinsic properties of a mixture|
|US6335527||Jan 13, 1999||Jan 1, 2002||SOLVAY S.A. (SOCIéTé ANONYME)||Device for monitoring latex properties during emulsion polymerization|
|US6534768||Oct 30, 2000||Mar 18, 2003||Euro-Oeltique, S.A.||Hemispherical detector|
|US6549861||Aug 10, 2000||Apr 15, 2003||Euro-Celtique, S.A.||Automated system and method for spectroscopic analysis|
|US6675030||Aug 17, 2001||Jan 6, 2004||Euro-Celtique, S.A.||Near infrared blood glucose monitoring system|
|US7238847||Dec 23, 2002||Jul 3, 2007||Shell Oil Company||Apparatus and method for determining and controlling the hydrogen-to-carbon ratio of a pyrolysis product liquid fraction|
|US7404411||Mar 23, 2005||Jul 29, 2008||Marathon Ashland Petroleum Llc||Method and apparatus for analysis of relative levels of biodiesel in fuels by near-infrared spectroscopy|
|US7659512||Jun 27, 2007||Feb 9, 2010||Dkk-Toa Corporation||Oil type discrimination method and oil type discriminator|
|US8148692 *||Aug 2, 2007||Apr 3, 2012||Sp3H||Method for ensuring the safety of the components of the drive train of a vehicle following the deterioration of the fuel|
|US8645079||Apr 14, 2010||Feb 4, 2014||Kuwait University||Method for measuring the properties of petroleum fuels by distillation|
|US8781757||Oct 10, 2008||Jul 15, 2014||Real-Time Analyzers, Inc.||Method and apparatus for determining properties of fuels|
|US8911512||Sep 20, 2012||Dec 16, 2014||Kior, Inc.||Use of NIR spectra for property prediction of bio-oils and fractions thereof|
|US9201053||Dec 13, 2013||Dec 1, 2015||Kuwait University||Method for measuring the properties of petroleum fuels by distillation|
|US9244052||Dec 17, 2012||Jan 26, 2016||Exxonmobil Research And Engineering Company||Global crude oil quality monitoring using direct measurement and advanced analytic techniques for raw material valuation|
|US20030102433 *||Jan 15, 2003||Jun 5, 2003||Ciurczak Emil W.||Hemispherical detector|
|US20040122276 *||Dec 23, 2002||Jun 24, 2004||Ngan Danny Yuk-Kwan||Apparatus and method for determining and contolling the hydrogen-to-carbon ratio of a pyrolysis product liquid fraction|
|US20050033127 *||Jan 27, 2004||Feb 10, 2005||Euro-Celtique, S.A.||Wireless blood glucose monitoring system|
|US20050256352 *||Apr 15, 2003||Nov 17, 2005||Clark Richard H||Method to increase the cetane number of gas oil|
|US20060213554 *||Mar 23, 2005||Sep 28, 2006||Marathon Ashland Petroleum Llc||Method and apparatus for analysis of relative levels of biodiesel in fuels by near-infrared spectroscopy|
|US20070050154 *||Sep 1, 2005||Mar 1, 2007||Albahri Tareq A||Method and apparatus for measuring the properties of petroleum fuels by distillation|
|US20070212790 *||Jan 19, 2007||Sep 13, 2007||Marathon Petroleum Company Llc||Method for monitoring feeds to catalytic cracking units by near-infrared spectroscopy|
|US20090145392 *||Nov 25, 2008||Jun 11, 2009||Clark Richard Hugh||Fuel formulations|
|US20090279072 *||Jun 27, 2007||Nov 12, 2009||Dkk-Toa Corporation||Oil type discrimination method and oil type discriminator|
|US20100007874 *||Aug 2, 2007||Jan 14, 2010||Sp3H||Method for ensuring the safety of the components of the drive train of a vehicle following the deterioration of the fuel|
|US20100204925 *||Aug 12, 2010||Tareq Abduljalil Albahri||Method for measuring the properties of petroleum fuels by distillation|
|US20100211329 *||Oct 10, 2008||Aug 19, 2010||Stuart Farquharson||Method and apparatus for determining properties of fuels|
|US20100305872 *||May 31, 2009||Dec 2, 2010||University Of Kuwait||Apparatus and Method for Measuring the Properties of Petroleum Factions and Pure Hydrocarbon Liquids by Light Refraction|
|CN100443883C||Nov 20, 2006||Dec 17, 2008||扬子石油化工股份有限公司||Method for detecting hydrgenated tail-oil paraffin composition using near-infrared spectrum|
|CN100451615C||Nov 20, 2006||Jan 14, 2009||扬子石油化工股份有限公司||Method for detecting hydrogenated tail-oil cyclanes and arene composition using near infrared spectrum|
|EP0732580A2 *||Mar 12, 1996||Sep 18, 1996||Ohmeda Inc.||Apparatus for automatic identification of gas samples|
|EP2949732A1||May 28, 2015||Dec 2, 2015||Shell Internationale Research Maatschappij B.V.||Use of an oxanilide compound in a diesel fuel composition for the purpose of modifying the ignition delay and/or the burn period|
|WO1999002973A1 *||Jul 9, 1997||Jan 21, 1999||Ashland Inc||Process and apparatus for analysis of hydrocarbon species by near infrared spectroscopy|
|WO2001002088A1 *||Jul 4, 2000||Jan 11, 2001||Neste Chemicals Oy||Method for the control of the manufacturing process of polyols|
|WO2003087273A1 *||Apr 15, 2003||Oct 23, 2003||Richard Hugh Clark||Method to increase the cetane number of gas oil|
|WO2013083596A1||Dec 5, 2012||Jun 13, 2013||Shell Internationale Research Maatschappij B.V.||New use|
|WO2013093100A1||Dec 21, 2012||Jun 27, 2013||Shell Internationale Research Maatschappij B.V.||Organic nitrates as ignition enhancers|
|WO2014037439A1||Sep 5, 2013||Mar 13, 2014||Shell Internationale Research Maatschappij B.V.||Fuel composition|
|WO2014096234A1||Dec 19, 2013||Jun 26, 2014||Shell Internationale Research Maatschappij B.V.||Liquid diesel fuel compositions containing organic sunscreen compounds|
|WO2015157207A1||Apr 7, 2015||Oct 15, 2015||Shell Oil Company||Diesel fuel with improved ignition characteristics|
|WO2015189218A1 *||Jun 9, 2015||Dec 17, 2015||Topnir Systems Sas||Method for optimising a mixture of constituents by means of spectral analysis|
|U.S. Classification||250/339.12, 250/343|
|International Classification||G01N21/27, G01N33/22, G01N21/35, G01N33/28|
|Cooperative Classification||G01N21/3577, G01N33/2829, G01N2201/129, G01N21/359|
|European Classification||G01N21/35G, G01N33/28F|
|Apr 9, 1990||AS||Assignment|
Owner name: ASHLAND OIL INC., ASHLAND, KENTUCKY A CORP OF COMM
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:MAGGARD, STEVEN M.;REEL/FRAME:005361/0862
Effective date: 19900409
|Mar 3, 1998||FPAY||Fee payment|
Year of fee payment: 4
|Nov 29, 2001||FPAY||Fee payment|
Year of fee payment: 8
|Sep 26, 2005||FPAY||Fee payment|
Year of fee payment: 12
|Apr 4, 2012||AS||Assignment|
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC;REEL/FRAME:027987/0608
Effective date: 20080903
Owner name: MARATHON PETROLEUM COMPANY LLC, OHIO